Project Se(L)ect(i)vity (PTDC/EQU-EQU/6193/2020)

Profiled membranes (also known as corrugated membranes, micro-structured membranes, patterned membranes, membranes with designed topography or notched membranes) are gaining increasing academic and industrial attention and recognition as a viable alternative to flat membranes. So far, profiled ion exchange membranes have shown to significantly improve the performance of reverse electrodialysis (RED), and particularly, electrodialysis (ED) by eliminating the spacer shadow effect and by inducing hydrodynamic changes, leading to ion transport rate enhancement. The beneficial effects of profiled ion exchange membranes are strongly dependent on the shape of their profiles (corrugations/patterns) as well as on the flow rate and salts’ concentration in the feed streams. The enormous degree of freedom to create new profile geometries offers an exciting opportunity to improve even more their performance. Additionally, the advent of new manufacturing methods in the membrane field, such as 3D printing, is anticipated to allow a faster and an easier way to create profiled membranes with different and complex geometries.

Salinity gradient energy is currently attracting growing attention among the scientific community as a renewable energy source. In particular, Reverse Electrodialysis (RED) is emerging as one of the most promising membrane-based technologies for renewable energy generation by mixing two solutions of different salinity. This work presents a critical review of the most significant achievements in RED, focusing on membrane development, stack design, fluid dynamics, process optimization, fouling and potential applications. Although RED technology is mainly investigated for energy generation from river water/seawater, the opportunities for the use of concentrated brine are considered as well, driven by benefits in terms of higher power density and mitigation of adverse environmental effects related to brine disposal. Interesting extensions of the applicability of RED for sustainable production of water and hydrogen when complemented by reverse osmosis, membrane distillation, bio-electrochemical systems and water electrolysis technologies are also discussed, along with the possibility to use it as an energy storage device. The main hurdles to market implementation, predominantly related to unavailability of high performance, stable and low-cost membrane materials, are outlined. A techno-economic analysis based on the available literature data is also performed and critical research directions to facilitate commercialization of RED are identified.

The power density obtainable by a reverse electrodialysis (RED) stack decreases along its operating period due to fouling; however this effect is not accounted for by the so far proposed mechanistic models. Recently, it has been demonstrated that 2D fluorescence spectroscopy can capture the time evolvement of ion-exchange membrane fouling. In this work multivariate statistical modeling was performed, by using the projection to latent structure (PLS) approach, to predict relevant RED stack performance parameters: pressure drop, stack electric resistance and net power density. Several PLS models, with and without 2D fluorescence data as models inputs, were developed. It was found that inclusion of fluorescence data considerably improved the models fitting, because the otherwise missing information about the dynamic state of ion-exchange membranes was added. Additionally, the coefficients of the optimized models revealed important contributions of some of the input parameters to the predicted outputs and allowed to mathematically confirm the qualitative observations that fouling of anion-exchange membranes facing river water is the main factor affecting the RED stack performance. This work confirms the applicability of 2D fluorescence spectroscopy for monitoring of fouling in RED stacks and demonstrates the ability of simple, statistically based models to follow RED performance.

Reverse electrodialysis (RED) is a sustainable technology for salinity gradient energy harvesting. In order to make the process economically competitive, it is desirable to operate it at the highest possible net power density, which depends on the RED stack geometry and on the pressure drop along its pathways and, thus, on the energy spent for solutions pumping. The fluid flow in RED stacks generally occurs in rectangular compartment channels, equipped with spacers. The effects of spacers design and properties have been studied extensively in recent years. However, the other possible causes for a RED stack and their relative impact on the process performance have not yet been systematically studied. In this study the partial pressure drops in (1) distribution ducts, (2) branches, (3) beams, (4) due to sudden section expansion between the beam and the compartment channel and (5) in the compartment channel were taken into consideration. A model for the total pressure drop inside a RED stack, with a parallel fluid flow distribution through the compartments, is proposed and experimentally validated for lab-scale RED stacks with sheet flow spacers and compared with an open channel (spacer-free) design. The importance of each partial pressure drop was then evaluated quantitatively through model simulations for industrial-scale stacks with an increasing number of cell pairs. It was found that the net power density decreases when the cell-pair number increases, since the partial pressure drop in the branches becomes dominant. Moreover, the possible reasons for a non-uniform fluid flow distribution are discussed, thus making the proposed model useful for planning and/or optimization of RED stacks design.